ES2335151T3 - NEW POLYSYLOXANES WITH QUATERNARY AMMONIUM GROUPS, PROCEDURES FOR THEIR PREPARATION AND THEIR USE IN CLEANING AND CARING FORMULATIONS. - Google Patents

Abstract

Polysiloxanes of the general formula I ** (See formula) ** Formula I in which the substituents and indices mean: ** (See formula) ** the X = same or different organic radicals, which carry ammonium functions the Y = same or different radicals taken from the group consisting of alkyl, aryl or alkylaryl with 1 to 30 C atoms, Z = same or different radicals taken from the set consisting of alkyl, aryl or alkylaryl with 1 to 30 C atoms, n = of 2 to 200

Description

New polysiloxanes with ammonium groups Quaternaries, procedures for their preparation and use in cleaning and care formulations.

The invention relates to new ones polysiloxanes with quaternary ammonium groups, as well as a Procedure for its preparation. It also refers to the use of these polymers as an additive in formulations for the care, conservation and cleaning of the skin and of structures attached to the skin, such as for example as conditioning agent for hair, as well as for cleaning and the care of hard surfaces, such as as an additive in the washing of motor vehicles.

Certain polysiloxanes with quaternary groups and its application as additives for the care and conservation of hair or as softening agents of textile materials are known from the patent literature. For example, in the publication document for appeal to oppositions of the German patent application DE AS 14 93 384 describes some structures, in which some siloxanes are modified in lateral positions with distributed ammonium groups statistically throughout the polymer. These compounds have the disadvantage that a pronounced character of silicone and you can no longer see a good efficacy.

A pronounced silicone character have it cationic silicones, such as those described in the German patent document DE 37 19 086 and in the European patent document EP 0 282 720. EP 0 282 720 describes structures, in which quaternary functions are united in the ends with siloxane. Such compounds offer advantages in which refers to its effect as a conditioning agent for both hair and textile materials as well as surfaces hard. Here, however, only two centers are available cationic, which often leads only to a insufficient substantivity on the surface.

From the publication document of German patent application DE-OS 33 40 708 se they know polymers of polyquaternary polysiloxanes. The polyquaternary polysiloxane polymers of this type no They have the disadvantages described above. To use in the practice of these compounds opposes, however, their expensive Preparation procedure The compounds can be prepared with yields of <60% of theorists, which are not financially bearable.

Human hair is subjected daily to the most different influences. Along with some requests mechanics by brushing, combing, lifting or retrofixation, the hair is also attacked by influences from the environment, such as strong radiation from UV (ultraviolet), cold, wind and water. Also the state physiological (eg age, health) of the respective person It influences the state of keratin fibers.

In particular, treatment with agents chemical modifies the structure and surface properties of the hair Methods, such as ripple for example permanent, bleaching, staining, shading, smoothing, etc., but also frequent washing with surfactants aggressive, contribute to cause more deterioration or less large in the hair structure. For example, in the case of a permanent undulation both the cortex is attacked (cortex) as well as the hair cuticle. The bridges of Cystine disulfide are broken by the reduction stage and they are oxidized in the subsequent oxidation stage partly to form cysteinic acid

Whitening not only destroys melanin but also oxidizes approximately 15 to 25% of the cystine disulfide bonds in the case of mild bleaching. In the case of excessive bleaching, this proportion may even be up to 45% (KF of Polo, A Short Textbook of Cosmetology, 2000, Verlag für chemische Industrie [Editorial for the chemical industry], H. Ziolkowsky
GmbH).

Thus, from chemical treatments, the frequent washing or of the disadvantageous mechanical properties of the UV irradiation for hair, which has been caused by removal of capillary fat or agents of moisture retention of hair, which are segregated in a way natural (sebum). In this way they become fragile, dry, tarnished, porous and badly combed.

In addition, thoroughly cleaned hair is usually very difficult to comb, both in a wet state and also in a dry state, since the individual hair They tend to curl and knot. So, these first to wash and then combing lose their ability to resistance. This is evident in a decrease significant tensile elongation resistance in the case of wet hair. In addition, these are less able to resist further deterioration caused by chemical agents, surfactants and environmental influences, which healthy hair

For the care and conservation of deteriorated hair in this way there are certain formulations specials, such as softener rinse agents of hair, hair curing agents, shampoos, stay conditioners (in English "leave in"), etc., which, however, can especially improve combing, the Touch and shine of damaged hair. Such agents for hair care and preservation, usual in the trade, mainly contain surfactants cationic based on compounds of alkyl ammonium, polymers, waxes or respectively silicone oils or oils. The effectiveness of these compounds is can attribute, among other things, to a hydrofugation of the hair surface.

In the cases of all these agents, it is achieved certainly a good care and conservation effect (conditioning) of hair, but through products conditioners are not improved, but even partially the appearance worsens, in particular the shine of the hair.

It remains, therefore, also a need for active substances that are suitable for use in multiple ways for cleaning, care and cleaning agents body, such as shampoos, hair treatment agents and post-hair treatment agents, which together with the cleansing effect improve hair preservation and les confer at the same time a good shine, to protect the hair with respect to the deterioration of the hair structure and minimize structural damage already caused to hair, caused by environmental influences as well as by treatments that confer shape and color.

A mission of the invention is to put provision of an active substance of this type, which is in a situation  to improve both properties and combing, the softness, volume, formability, workability, ability to unravel damaged hair and not impaired, as well as confer hair also a beautiful shine Compounds must therefore show a individual effect improved or at least as good, but in set an improved combined effect of mechanical properties and of other types.

Cleaning and care of hard surfaces in the private and industrial sector partly require complex formulations and regulated work courses, previously established. Thus, for example, the washing of motor vehicles In automatic washing facilities it is usually made up of several processes that take place consecutively, which They must be adapted exactly to each other. This adaptation includes, among other things, the correct choice of chemical formulations, respecting the time periods of performance, mechanical cleaning conditions and the choice of the temperatures. A larger bibliography is: F. Müller, J. Peggau, S. Arif, Special Purpose Cleaning Formulations: Auto Care [cleaning formulations for special uses: care automatic], in Handbook of Detergents, Part D: Formulation [Manual of detergents, part D: formulation], M. Showell, coordinator of edition] CRC Press, Boca Raton 2006, pages 261 to 278.

The cleaning itself, which can be subdivided into a previous wash and a main wash, being able to different base formulations are used in each case, it includes the removal of solid and insoluble dirt particles on the surface of the vehicle. For this, there is a large number of formulations for the most different cleaning procedures. These formulations are usually composed of systems of anionic surfactants, which together with basic or acidic components provide tensioactivity That is necessary for cleaning.

This cleaning is followed by the rinsing process, in which the remains of the cleaning agent must be removed. This stage serves for the previous preparation for the use of an appropriate drying agent, which, before final drying by blown, water repellent to the vehicle and thus be eliminated more easily the remaining water film. The rinse is important therefore, since desiccants have a cationic character and otherwise, after use of anionic cleaning formulations, would form salts hardly soluble, which lead on the vehicle to stains of bad appearance, and thus do not lead to the desired effect of shine or water repellent.

Cationic surfactants, in the case of some applications where a substantivity is requested, is say a permanence of the compound with surface activity on the treated material, constitute the ingredient substances Essentials of these formulations. As in the case of applications in the sector of softening agents, the preparation of textile materials or hair rinsing agents, this substance class therefore finds its spread also in the case of desiccant agents in automatic washing facilities Of automobiles.

Since also varnishes for vehicles, such as for most surfaces, they have a negative electrical potential, after application by atomization of the desiccant agent formulation, the agents cationic surfactants spread over the vehicle and displace the water film that is present. This process that is designated as "break" (in German "Aufriss"), gives as resulted in an association of the water film to form drops. These drops then fall so much by the force of gravity itself as well as the use of a fan in the last stage of the automatic vehicle cleaning.

The formulation of auxiliary agents of the drying for automatic vehicle cleaning, puts professional formulator before special missions. So, the formulation should not only generate a spontaneous rupture of the water, but should also lead to rapid drying and a long persistent shine. It is important in this case the correct concentration of use, which should be located from approximately 0.1 to 0.3%. If the concentration is too low, then the water film will not break, and if it is too high, then a layer will form on the surface of the vehicle greasy and unctuous, which can no longer lead to the desired effect of brightness.

The formulation must remain, even at very Low temperatures, clear, transparent and without precipitation. In addition to this, the product must have a high tolerance facing the hardness of water, in order not to lead to cloudiness neither in the case of hard and soft waters, nor neither in a water treated renewedly. Waxes, oils or other care and conservation agents, not miscible with water, which eventually they are used, which must remain on the surface, They have to emulsify.

A basic formulation for a desiccant agent It is composed as a rule of quaternary ammonium compounds, the so-called cuates (Spanishization of English quats). In this context, esters are now almost exclusively used - cuates or imidazolines - cuates, which are respectful to the environment environment, in which the chain of a fat is composed mainly oleic acid. The four, for the most part, do not they are soluble in water, these highly unsaturated chains facilitate the formulation in aqueous systems.

Together with the friends, some are also needed raw materials with emulsifying properties, in order to guarantee the aforementioned requirements profile.

In the course of the acceleration of the automatic washing train operation, have been undertaken various attempts to accelerate the breakage process, which is relatively long and tedious. For example, some were tested silicone compounds, such as those described in the Document DE 101 07 772, but without any success. Since one of the speed determining stages in the wash train automatic is the runoff of the desiccant agent, a acceleration will increase the flow rate of vehicles in the train washing, and therefore will reduce waiting times for customers and will increase the efficiency of the installation.

This invention is based on the mission of find some quaternary polysiloxane polymers, which can prepare with good yields and in addition in the respective applications present the desired property profile and show a very conditioning effect and a very good shine on the hair

This invention is also based on the mission of find some quaternary polysiloxane polymers, which can prepare with good yields and in addition to this present in the respective applications the desired property profile, as well as having a manifestly accelerated break along with a simultaneous brightness conservation in the automatic care of motor vehicles

Surprisingly, it was found that some polysiloxanes of the general formula I [M 'D n] 3 T They provide this result.

An object of the invention are therefore about polysiloxanes of the general formula I

one

Formula I

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In this case it is realized that:

2

the X

they are the same or different organic radicals, which they carry ammonium functions,

The and

they are the same or different radicals taken from set consisting of alkyl, aryl or alkylaryl with 1 to 30 atoms of C, preferably methyl or phenyl, in particular methyl,

the Z

they are the same or different radicals taken from set consisting of alkyl, aryl or alkylaryl with 1 to 30 atoms of C, preferably methyl or phenyl,

n

is from 2 to 200, preferably from 3 to 120, in particular from 8 to 80.

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Appropriate X radicals are, for example, some groups that have the structure -R1-R2, in the that

the R1

they are preferably equal divalent radicals or different, selected from the set consisting of

3

R1

It is preferably:

4

R2

is selected from the set that is composed from

5

the R3

they are the same or different radicals, taken from set consisting of hydrogen or alkyl with 1 to 6 atoms, of preferred way methyl,

the R4

they are divalent hydrocarbyl radicals, the same or different, which eventually contain ether functions, of preferred way methylene,

R5, R6 and R7 are, in each case independently of each other hydrogen or alkyl radicals with 1 to 30 atoms of C,

the R8

they are the same or different radicals taken from set consisting of -O-; -NR10,

the R9

they are divalent hydrocarbyl radicals eventually branched, same or different,

the R10

they are the same or different radicals, taken from set consisting of hydrogen or alkyl with 1 to 6 atoms of C,

the R11

they are the same or different radicals of the formula general:

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6

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the R12

are aryl alkyl or alkylaryl radicals with 1 to 30 C atoms, the same or different, that eventually contain ether functions, preferably are methyl, ethyl or phenyl, in particular methyl,

and

is from 0 to 20, preferably from 0 to 10, in particular from 1 to 3,

F

is from 0 to 20, preferably from 0 to 10,

e + f> = 1,

x

is from 2 to 18,

to

is from 2 to 18, preferably 3,

the A <->

they are the same or different ions of the opposite sign regarding the positive charges with the groups quaternized nitrogen, which are selected from anions inorganic or organic HA acids, as well as their derivatives.

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It is familiar to an expert in the specialty that the compounds are presented in the form of a mixture with a distribution that is essentially regulated by laws statistics

The unit T is present in the average statistical once in a polymer chain. However, it it presents a mixture of molecules, so that a certain proportion of the molecules do not possess any T unit or possess Several of them.

In another preferred embodiment of the present invention, the opposite sign A ion with respect to the positive charges with quaternized nitrogen groups, It consists of the anion of a physiologically compatible HA acid, which it is especially preferably selected from acid acetic acid L-hydroxycarboxylic acid, in particular lactic acid, or aromatic carboxylic acids.

Other preferred counter ions they come from usual quaternization agents. These are in particular ethyl sulfate, methyl sulfate, toluene sulphonate, chloride and bromide.

A further object of this invention is a procedure for the preparation of products conforming to invention. This part of the balance of a aryl-tris (dimethylsiloxy) silane and / or an alkyl-tris- (dimethylsiloxy) silane, in particular of phenyl-tris- (dimethylsiloxy) silane and of methyl-tris (dimethylsiloxy) -silane, with octamethyl-cyclootetraxiloxane and / or Decamethyl-cyclopentasiloxane (cyclic compounds). Appropriate methods for siloxane equilibrium are described for example in EP 1 439 200.

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Together with cyclic siloxanes, they can be added to the perform the balance, also some siloxanes with functions α- \ omega-di-SiH or non-functional siloxanes to the equilibrium mixture, with the in order to deliberately decrease the average degree of modification.

With siloxanes that have SiH functions, so obtained, you can then hydrosilylate epoxides that they contain double bonds, such as for example allyl glycidyl ether. It is known to an expert in the specialty used for hydrosilylation Pt, Rh or Ru catalysts.

The epoxy-siloxanes as well obtained can finally be reacted with amines tertiary to give the desired function-carrying siloxanes of quaternary ammonium.

It is known to an expert in the specialty the fact that within the framework of such a sequence of reactions there are to have side reactions, both when performing the balancing silanes with SiH functions, as well as perform hydrosilylation and quaternization. The extent of the side reactions depends, among other things, on the type of eductos (starting products) as well as the conditions of reaction. Thus, for example, the degree of quaternization at carry out the reaction of epoxy siloxanes with amines tertiary in the presence of carboxylic acids, according to Current methods is located at approximately 80 to 95%.

A further object of this invention is the use of the compounds of the general formula I, and of the compounds of the general formula I that have been prepared according with the process according to the invention, or respectively of the technical mixtures produced in accordance with this procedure, such as an additive in care, conservation and cleaning formulations, which eventually contain surfactants.

A further object of this invention is the use of the compounds of the general formula I, and of the compounds of the general formula I that have been prepared according with the process according to the invention, or respectively of the technical mixtures produced in accordance with this procedure, such as a conditioning agent for treatment agents of the hair and for post-hair treatment agents, as well as as agents for the improvement of the hair structure.

A further object of this invention is the use of the compounds of the general formula I, and of the compounds of the general formula I that have been prepared according with the process according to the invention, or respectively of the technical mixtures produced in accordance with this procedure, for the production of care and conservation formulations, brightness enhancers.

An additional object of this invention is they constitute agents for the treatment of hair and some agents for the subsequent treatment of hair, intended for the separation by rinsing or for the permanence in the hair, for example shampoos with or without a pronounced conditioning effect, 2-in-1 type shampoos, rinsing agents, curing agents of the hair, masks for the hair, auxiliary agents of hairdresser, styling agents, secape lotions, hair strengthening agents, corrugating agents permanent, hair straightening agents and agents for Dye your hair. Depending on the purpose of application, such agents containing 2 to 25% by weight of one or more agents active surfactants for washing (detergents) taken from set consisting of anionic surfactants, not ionic, amphoteric or ionic hybrids, 0.5 to 10% by weight of one or various emulsifying agents, from 0.5 to 10% by weight of one or more agents that confer consistency, from 0.5 to 10% by weight of one or various surfactants or emulsifiers preferably cationic, 1 to 20% by weight of one or more cosmetic oils silicone oils or emollients, as well as usual substances auxiliary and additive in usual concentrations, and that additionally contain one or more cosmetic active substances for hair, chosen from the set of polymers cationics such as for example quaternized celluloses and their derivatives, chitosan and its derivatives, cationic alkyl glycosides, cationic derivatives of guar, salt-based polymers of dimethyl diallyl ammonium and its copolymers with esters and amides of acrylic acid and acid methacrylic, vinyl pyrrolidone copolymers with quaternized derivatives of acrylates and methacrylates of dialkyl amino alkyls, such as for example vinyl pyrrolidone copolymers and dimethyl amino amino methacrylate, quaternized for example with diethyl sulfate, copolymers of vinyl pyrrolidone and methochloride vinyl imidazolium, terpolymers based on vinyl pyrrolidone, caprolactam and monomers acrylamides, a quaternized polyvinyl alcohol as well as polymers that are known under the INCI designations Polyquaternium-2, Polyquaternium-17,  Polyquaternium-18, Polyquaternium-27 and Polyquaternium-37, hydrolyzed materials of proteins, cationic or non-ionic, of plant or animal origin, Based on keratin, collagen, elastin, wheat, rice, soybeans, milk, silk, corn or other silicon derivatives, such as by example Dimethiconol or Dimethicone (INCI designations for poly (dimethylsiloxanes)) as well as modified silicones that may be terminal functionalized (INCI bis- prefix) and / or functionalized by grafting, since they are found there by example alkoxy silicones and alkyl silicones with alkyl groups of chains long, poly (oxyalkyl) modified silicones as PEG / PPG-3/10 Dimethicone or bis-PEG / PPG-20/20 Dimethicone with or without an alkyl ether group, and its esters, such as for example Dimethicone PEG-7 Cocoate, as well as silicones multifunctionalized, such as for example Cetil PEG / PPG-10/1 Dimethicone or Methylene Phenyl PEG-8 Dimethicone, and in addition to this copolymers of silicones with acrylates, including such copolymers with or without alkyl modification, branched silicon derivatives such as dimethicone and silsesquioxane copolymers, copolymers silicon crosslinks such as a crosslinked polymer of Dimethicone, a crosslinked polymer of Alkyl Dimethicones and Divinyl Dimethicone, a crosslinked polymers of Cetethyl Dimethicone or a crosslinked polymer of Cetearyl Dimethicone and Vinyl Dimethicone, silicones with amino functions such as Amodimethicone, Aminopropyl Dimethicone, PEG-7 Amodimethicone, Methoxy PEG / PPG-7/3 Aminopropyl Dimethicone, or silicones ionically modified such as Dimethicone Propyl PG-Betaines, vitamins, panthenol, acid pyrrolidone-carboxylic acid, bisabolol, extracts of plants (vegetables), creatine, ceramides, as well as agents that absorb UV rays, they are characterized because they contain an effective amount of at least one compound of the formula general (I).

A further object of this invention is the use of the compounds of the general formula I and of the compounds of the general formula I, which have been prepared according with the process according to the invention, or respectively of the technical mixtures produced in accordance with this procedure, for the production of formulations intended for cleaning and care of hard surfaces, preferably for cleaning and car care, particularly as an additive in auxiliary drying agents for washing trains automatic.

Examples of realization

The following Examples should serve for the explanation of the invention, but they do not constitute any kind of limitations

Example 1 a) Balancing a polysiloxane with functions Yes H

In a three-mouth flask with a capacity of 500 ml, 8.2 g of phenyltris (dimethylsiloxy) -silane, 334 g of decamethyl-pentasiloxane and 0.34 g of a catalyst acidic, and stirred at 80 ° C for 4 hours. After the cooling, 20 g of NaHCO3 was added, and stirred for 12 hours at room temperature. After a filtration, it obtained a clear and transparent product with a SiH value of 0.02%

b) Preparation of an epoxy siloxane

In a three-mouth flask with a capacity of  500 ml 300 g of the compound were previously arranged in common prepared within Example 1 a) and 7.5 g of a alkyl glycidyl ether and heated to 100 ° C. TO then 15 ppm of a platinum catalyst was added and stirred for two hours. After a subsequent reaction, it obtained a clear and transparent product with an epoxy value of 0.37%.

c) Chemical conversion in the polysiloxane polymer quaternary

In a three-mouth flask with a capacity of  500 ml were stirred at room temperature 14.5 g of 3-N, N-dimethyl-aminopropyl amide  of lauryl acid, 2.7 g of acetic acid and 120 g of isopropanol. Then 200 g of the compound were added dropwise prepared according to Example 1 b). Then stirred for 8 hours at 50 ° C and it was distilled. A cloudy liquid was obtained highly viscous, which is described by the following formula statistics:

7

It is familiar to an expert in the specialty that the above formula constitutes a structural formula idealized In the product structures are additionally presented linear and more highly branched.

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Example 2 a) Balancing a polysiloxane with functions Yes H

In a three-mouth flask with a capacity of 1,000 ml, 50 g of mixed phenyltris (dimethyl siloxy) -silane,  667 g of decamethyl-pentasiloxane and 0.7 g of a acid catalyst, and stirred at 80 ° C for 4 hours. After cooling, 15 g of NaHCO3 were added, and stirred for 12 hours at room temperature. after one filtration a transparent product with a SiH value of 0.07%

b) Preparation of an epoxy siloxane

In a three-mouth flask with a capacity of 1,000 ml 670 g of the compound were previously arranged in common prepared within Example 2 a) and 65 g of allyl glycidyl ether, and heated to 100 ° C. TO 15 ppm (parts per million) of a Platinum catalyst and stirred for two hours. after one subsequent reaction, a clear and transparent product was obtained with an epoxy value of 0.99%.

c) Chemical conversion in silicone silicone

In a three-mouth flask with a capacity of 1,000 ml was stirred at room temperature 63 g of N, N-dimethyl-stearyl-amine,  12 g of acetic acid and 200 g of isopropanol. Then you 325 g of the compound prepared according to the Example 2 b). It was then stirred for 8 hours at 60 ° C and was distilled A highly viscous turbid liquid was obtained, which is described by the following statistical formula:

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8

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It is familiar to an expert in the specialty that the above formula constitutes a structural formula idealized In the product structures are additionally presented linear and branched to a higher degree.

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Example 3 a) Balancing a polysiloxane with functions Yes H

In a three-mouth flask with a capacity of  500 ml, 33.1 g of phenyltris (dimethyl siloxy) silane, 274.4 g of decamethyl-pentasiloxane and 0.3 g of a acid catalyst, and stirred for 4 hours at 80 ° C. After cooling, 10 g of NaHCO3 was added and stirred for 12 hours at room temperature. after one filtration, a clear and transparent product with a value was obtained SiH of 0.097%.

b) Preparation of an epoxy siloxane

In a three-mouth flask with a capacity of 250 ml 103.5 g of the compound were previously arranged in common prepared according to Example 3 a) and 15 g of allyl glycidyl ether, and heated to 100 ° C. TO 15 ppm of a platinum catalyst was then added, and stirred for two hours. After a subsequent reaction obtained a clear and transparent product with an epoxy value of 1.4%

c) Chemical conversion in silicone silicone

In a three-mouth flask with a capacity of 500 ml was stirred at room temperature 32 g of 3-N, N-dimethyl-aminopropyl amide  of lauryl acid, 6.2 g of acetic acid and 100 g of isopropanol. Then, 115 g of the compound were added dropwise prepared according to Example 3 b). It was then stirred for 8 hours at 60 ° C and distilled. A highly cloudy liquid was obtained viscous, which is described by the following statistical formula:

9

It is familiar to an expert in the specialty that the above formula constitutes a structural formula idealized In the product structures are additionally presented linear and branched to a higher degree.

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Example 4 a) Balancing a polysiloxane with functions Yes H

In a three-mouth flask with a capacity of  500 ml, 3.3 g of phenyltris (dimethyl siloxy) silane, 220.4 g of decamethyl-pentasiloxane and 0.3 g of a acid catalyst, and stirred for 4 hours at 80 ° C. After cooling 4.5 g of NaHCO3 were added and stirred at room temperature for 12 hours. after one filtration a transparent product with a SiH value of 0.013%

b) Preparation of an epoxy siloxane

In a three-mouth flask with a capacity of 1,000 ml 752 g of the compound were previously arranged in common prepared according to Example 4 a) and 14.8 g of allyl glycidyl ether, and heated to 100 ° C. TO 15 ppm of a platinum catalyst was then added, and stirred for two hours. After a subsequent reaction obtained a clear and transparent product with an epoxy value of 0.21%.

c) Chemical conversion in silicone silicone

In a three-mouth flask with a capacity of  250 ml were stirred at room temperature 3.2 g of 3-N, N-dimethyl-aminopropyl amide  of lauryl acid, 0.62 g of acetic acid and 50 g of isopropanol. Then 76.2 g of the compound were added dropwise prepared according to Example 4 b). It was then stirred for 8 hours at 60 ° C and distilled. A highly cloudy liquid was obtained viscous, which is described by the following statistical formula:

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10

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It is familiar to an expert in the specialty that the above formula constitutes a structural formula idealized In the product structures are additionally presented linear and branched to a higher degree.

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Example 5 a) Balancing a polysiloxane with functions Yes H

In a three-mouth flask with a capacity of  500 ml, 6.7 g of methyltris (dimethyl siloxy) silane, 334 g of decamethyl-pentasiloxane, 0.4 g of a acid catalyst, and stirred for 5 hours at 80 ° C. After cooling, 20 g of NaHCO3 were added, and stirred at room temperature for 12 hours. after one filtration a clear and transparent product with a value was obtained of SiH of 0.02%.

b) Preparation of an epoxy siloxane

In a three-mouth flask with a capacity of 1,000 ml 450 g of the compound were previously arranged in common prepared according to Example 5 a) and 11.3 g of allyl glycidyl ether, and heated to 100 ° C. TO then 15 ppm of a platinum catalyst was added and stirred for two hours. After a subsequent reaction obtained a clear and transparent product with an epoxy value of 0.37%.

c) Chemical conversion in the polysiloxane polymer quaternary

In a three-mouth flask with a capacity of 1,000 ml were stirred at room temperature 31.9 g of 3-N, N-dimethyl-aminopropyl amide  of lauryl acid, 8.9 g of lactic acid and 200 g of isopropanol. Then 440 g of the compound were added dropwise prepared according to Example 5 b). It was then stirred for 8 hours at 50 ° C and distilled. A highly cloudy liquid was obtained viscous, which is described by the following statistical formula:

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eleven

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It is familiar to an expert in the specialty that the above formula constitutes a structural formula idealized In the product structures are additionally presented linear and branched to a higher degree.

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Technical properties of applications Application in cosmetics

Production and testing of agents for hair treatment mediating compound utilization 1, 2, 3, 4, 5 according to the invention.

For the technical evaluation of applications, some hair braids, which are used for sensory tests, are previously deteriorated in a normalized way by permanent ripple treatment and a bleaching treatment. For this, some usual products were used in hairdressing. He course of the tests, the base materials used as well as details of the evaluation criteria, they are described in the DE 103 27 871.

Recipe Recipes

For the technical evaluation of applications, use the compounds according to the invention and comparative products  in simple cosmetic formulations.

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The application properties in the case of Use in a shampoo were checked in the following recipe:

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12

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For the evaluation of the properties of the shampoo formulation was not carried out in the course of Test any further treatment with a rinse agent.

In addition to this, the products conform to the invention was also checked in a simple rinse agent of hair with the following constitution:

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13

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The pretreatment of the hair was carried out in the case of checking the properties of agents of Rinse the hair, using a shampoo, which does not contain any conditioning agent

As "conditioning agents" are designated Examples of compounds according to the invention, products comparatives or combinations of compounds according to the invention and known conditioning agents (in particular Chloride Cetrimony).

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Standardized treatment of hair tufts previously deteriorated with conditioning samples:

Locks of previously damaged hair or As described above, they are treated as follows with the shampoo described above or with the conditioning rinse agent described above. The tufts of hair are wet under water warm flowing. Excess water is lightly squeezed to hand, then the shampoo is applied and incorporated gently into the hair (1 ml / tufts of hair (2 g)). After a period of permanence of 1 min, the hairs are rinsed for 1 min. Eventually, it applies directly to then the rinse agent and gently incorporated into the hair (1 ml / tufts of hair (2 g)). After a period of residence time of 1 min, the hair is rinsed during 1 min

Before sensory evaluation of hair they are air dried with an air humidity of 50% and at 25ºC for at least 12 hours.

The composition of the test formulations is deliberately choose in a simple way in order to avoid the influence on the test results by components of the formulations (normally present). Formulations according to the invention, together with the ingredients mentioned and / or instead of the mentioned ingredient substances They may still contain other ingredient substances. In in particular, the combination with other ingredient substances Additional may lead, in the case of the described effects, to a synergistic improvement. Such ingredient substances can be (but you are not limited to them):

Surfactants, wetting agents or emulsifiers taken from the active substance sets superficially anionic, cationic, ionic hybrid, amphoteric or nonionic, such as (fatty alcohol) sulfates, (fatty alcohol) ether sulfates, alkyl sulfonates, alkyl benzene sulphonates, alkyl sulfosuccinates, quaternary salts of ammonium, alkyl betaines, (acid amido fatty) -alkyl-betaines, derivatives of monomeric or condensed saccharides, such as sugar esters, esters of methyl- or ethyl-glycoside-fatty acids, alkyl glycosides, ethoxylated fatty alcohols, alkanol-fatty acid amides or acid esters ethoxylated fatty acids, thickening agents, such as kaolin, Bentonite, fatty acids, fatty alcohols, starches, poly (acids acrylics) and their derivatives, cellulose derivatives, derivatives of guar, alginates, chitosan, petrolatum or a paraffin, and also cloud agents, such as ester derivatives glycols or alcohols such as ethanol, propanol, isopropanol, propylene glycol or glycerol, solubilizing agents, agents stabilizers, buffer systems, perfume oils (essential), dyes and in particular also additional ones conditioning agents and care additives, such as other cationic or amphoteric polymers, lanolin and its derivatives, cholesterol, ceramides, pantothenic acid, betaines, creatine, others silicones or derivatives of silicones.

Evaluation criteria

Sensory evaluations are made of agreement with qualification notes, which are awarded in a 1 to 5 scale, 1 being the worst rating and 5 the best assessment. Individual test criteria receive in each Case your own assessment.

The test criteria are: combability in wet, wet touch, dry comb, dry touch, appearance / brightness

The following table compares the results. of the sensory evaluation of the treatment of the tufts of hair, which is carried out as described above, with substances according to the invention or respectively with a placebo.

In the application as shampoos it was used as cationic polymer guar hydroxypropyl trimony chloride ("Guar-Quat" = guar's account).

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The results show, in a way surprisingly, that the compounds according to Examples 1 and 2, according to the invention, they obtain a significant assessment better than the comparative product "Quaternium-80". The compounds according to Examples 3 and 4, according to the invention, show an efficacy similarly good than Quaternium-80. It has been to highlight in a particularly clear way the good assessment of the gloss properties of all compounds conforming to invention.

fifteen

Also in the application as a rinse agent of the hair, the compounds according to the invention show in the sensory evaluation very good cosmetic evaluations. In that case, particularly in the assessments for wet touch and dry touch, performance is further increased, already good, Cetrimonium Chloride by combining with compounds according to the invention. An assessment significantly better is also achieved in the case of brightness.

In general, it is shown that the skin feeling in the hands is manifestly improved during and after application, when they are present in the formulations of compounds according to the invention. In particular, In the case of O / W emulsions (oil in water), the skin sensation by compounds conforming to invention.

Thus, in the formulation of the Examples, get a manifestly more pleasant feeling of the hair  by using the compounds according to the invention.

16

A further object of the invention is therefore the use of the compounds according to the invention for formulations for cleaning and skin care, such as shower products, bath products and liquid soaps.

Application in automatic car care

In addition, the use of compounds according to the invention in industrial automatic washing of automobiles, in auxiliary agents of desiccation in the train of automatic washing Here, after the cleaning stage, taken to out with anionic surfactants, it is subsequently connected a treatment with a cationic agent, which seeks brightness and hydrophobia on the varnish of the car and at the same time makes possible subsequent drying of the vehicle by means of a fan. The acting time of this agent is special importance in the case of automatic washing facilities, with the in order to increase the flow rate of vehicles and therefore efficiency The use of compounds according to the invention is checked in formulations adjusted to practice, observing surprisingly a considerable shortening of the time of breakage, also compared to quaternary compounds of silicones, known in the literature.

The following basic recipe was tested:

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Formulation 8

The basic recipe is formulation # 8.

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Formulation 9

The basic recipe with 0.8% of a substance active quaternary silicone compound according to the document  EP 0 294 643 is formulation 9.

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Formulation 10

The basic recipe with 0.8% of a substance active silicone quaternary compound according to this document with N = 50 is formulation 10.

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Formulation eleven

The basic recipe with 0.8% of a substance active silicone quaternary compound according to this document with N = 80 is formulation 11.

These formulations were diluted to 1: 1,000 with running water in a manner adjusted to practice, and dilutions were investigated in the breaking behavior.

It is characterizing the performance capacity the breakage of the water film on the varnish of the car as well as also on the glass surfaces of the vehicle after the addition of the auxiliary drying agent. While one Determination of breakage on varnished surfaces is difficult of reproducing, the surfaces of glass.

The breaking behavior was determined from the Following way:

The period of time, which is necessary, is measured in order to penetrate through a defined water film on a glass and remove the wetting of the glass. They hold on first reaction time period as well as displacement Total water from a slide.

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Reflective tile

Slide 76 x 26 mm (3 x 1 inches)

3 ml pipette synthetic material

100 \ mul dosing pipette

Water of defined quality:

conductivity indication

Chronometer

Bunsen burner.

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Samples are measured in a diluted state with water according to the indication, in most cases in a dilution of 1: 1000. The slide is dusted and previously flamed briefly by means of a flame, in order to guarantee a surface free of waste, absolutely clean.

0.5 ml of water are applied with the help of a pipette as a uniform film on the slide. If I dont know I should let any film form, the slide should be cleaned or discarded again. Then apply centrally on the water surface 50 µl of the dilution of use of the auxiliary drying agent, and the chronometer. The beginning of the elimination of wetting and penetration through the water that is removed over the side of 26 mm. In this way the period of reaction time and breaking rate.

The indication is made in seconds.

The Table shows the following results:

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It shows that, in particular, the break with the compound according to the invention with N = 50 has a considerable effect.

As staggering you can use the following table.

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The break should not end with too much speed, since otherwise micro droplets result hardly removable, leaving behind some vestiges after drying.

At the same time the compounds affect a visibly positive way about vehicle brightness dried

Claims (12)

1. Polysiloxanes of the general formula I twenty Formula I in which the substituents e indexes mean: twenty-one

the X =

same or different organic radicals, which they carry ammonium functions

the Y =

same or different radicals taken from the set formed by alkyl, aryl or alkylaryl with 1 to 30 atoms of C,

the Z =

same or different radicals taken from the set formed by alkyl, aryl or alkylaryl with 1 to 30 atoms of C,

n =

from 2 to 200.

2. Polysiloxanes according to claim 1, characterized in that X is = -R1-R2, with following meanings:

The R1

they are the same or different divalent radicals, selected from the set consisting of

22

R2

is selected from the set that is composed from

2. 3

the R3

they are the same or different radicals taken from set consisting of hydrogen or alkyl with 1 to 6 atoms C,

the R4

they are equal divalent hydrocarbyl radicals or different, which eventually contain functions of ether,

R5, R6 and R7 are, in each case independently of each other hydrogen or alkyl radicals with 1 to 30 atoms of C;

the R8

they are the same or different radicals taken from set consisting of -O-; -NR10,

the R9

they are divalent hydrocarbyl radicals eventually branched, same or different,

the R10

they are the same or different radicals taken between the set consisting of hydrogen or alkyl with 1 to 6 atoms of C

the R11

they are the same or different radicals of the formula general:

24

the R12

they are alkyl, aryl or alkylaryl radicals with 1 to 30 C atoms, the same or different, that eventually contain ether functions,

and

is from 0 to 20,

F

is from 0 to 20,

e + f> = 1,

x

is from 2 to 18,

to

is from 2 to 18,

the A <->

they are the same or different ions of the opposite sign in relation to positive charges with nitrogen groups quaternized, which are selected from inorganic anions or organic acids HA, as well as their derivatives.

3. Polysiloxanes according to claim 2, characterized in that R1 has the meaning 25 4. Process for the preparation of polysiloxanes according to one of claims 1 to 3, characterized in that aryltris (dimethylsiloxy) silanes and / or alkyltris- (dimethylsiloxy) silanes are first equilibrated with cyclic siloxane compounds, then epoxides containing Double bonds are hydrosilylated with the resulting balanced material having SiH functions and the epoxy-silanes thus obtained are finally reacted with tertiary amines to give the corresponding quaternary siloxanes. 5. Use of the compounds according to one of claims 1 to 3, as an additive in formulations aqueous care, conservation and cleaning, which eventually They contain surfactants. 6. Use of the compounds according to one of claims 1 to 3, as conditioning agents for hair treatment agents, treatment agents back of the hair and for the improvement of the structure of the hair. 7. Use of the compounds according to one of claims 1 to 3, for the production of care and conservation formulations, brightness enhancers. 8. Use of the compounds according to one of claims 1 to 3, for the production of formulations intended for skin cleansing. 9. Use of the compounds according to one of claims 1 to 3, for the production of formulations intended for the care and conservation of skin. 10. Use of the agreement compounds with one of claims 1 to 3, for the production of formulations intended for cleaning and surface care hard. 11. Use of the agreement compounds with one of claims 1 to 3, for the production of formulations intended for cleaning and car care cars 12. Use of the agreement compounds with one of claims 1 to 3, as an additive in agents dewatering aids for automatic washing trains of cars